Processing aid composition derived from a sulfinate-containing molecule

ABSTRACT

Described herein is a melt-processible polymer composition comprising: a non-fluorinated melt-processible polymer; and a fluoropolymer derived from the polymerization of a monomer and a sulfinate-containing molecule, wherein the sulfinate-containing molecule is selected from the group consisting of: (a) CX 1 X 3 ═CX 2 —(R) p —CZ 1 Z 2 —SO 2 M Formula (I) (b) Formula (II); and (c) combinations thereof, wherein X 1 , X 2 , and X 3  are each independently selected from H, F, Cl, a C 1  to C 4  alkyl group, and a C 1  to C 4  fluorinated alkyl group; R is a linking group; Z 1  and Z 2  are independently selected from F, CF 3 , and a perfluoroalkyl group; R 1  and R 2  are end-groups; p is 0 or 1; m is at least 2; and M is a cation.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage filing under 35 U.S.C. 371 ofPCT/US2012/068926, filed Dec. 11, 2012, which claims priority to U.S.Provisional Application No. 61/576,391, filed Dec. 16, 2011, thedisclosures of which are incorporated by reference in their entiretyherein.

TECHNICAL FIELD

The present disclosure relates to melt-processible polymer compositionsthat comprise a mixture of a non-fluorinated melt-processible polymerand a fluorine-containing polymer. The fluorine-containing polymer maybe used as a polymer processing aid.

BACKGROUND

For any melt processible thermoplastic polymer composition, there existsa critical shear rate above which the surface of the extrudate becomesrough and below which the extrudate will be smooth. See, for example, R.F. Westover, Melt Extrusion, Encyclopedia of Polymer Science andTechnology, Vol. 8, pp 573-81 (John Wiley & Sons 1968). The desire for asmooth extrudate surface competes, and must be optimized with respectto, the economic advantages of extruding a polymer composition at thefastest possible speed (i.e. at high shear rates).

Some of the various types of extrudate roughness and distortion observedin high and low density polyethylenes are described by A. Rudin, et al.,in Fluorocarbon Elastomer Aids Polyolefin Extrusion, PlasticsEngineering, March 1986, on 63-66. The authors state that for a givenset of processing conditions and die geometry, a critical shear stressexists above which polyolefins such as linear low-density polyethylene(LLDPE), high-density polyethylene (HDPE), and polypropylene suffer meltdefects. At low shear rates, defects may take the form of “sharkskin”, aloss of surface gloss that in more serious manifestations appears asridges running more or less transverse to the extrusion direction.

At higher rates, the extrudate can undergo “continuous melt fracture”becoming grossly distorted. At rates lower than those at whichcontinuous melt fracture is first observed, LLDPE and HDPE can alsosuffer from “cyclic melt fracture”, in which the extrudate surfacevaries from smooth to rough. The authors state further that lowering theshear stress by adjusting the processing conditions or changing the dieconfiguration can avoid these defects to a limited extent, but notwithout creating an entirely new set of problems.

For example, extrusion at a higher temperature can result in weakerbubble walls in tubular film extrusion, and a wider die gap can affectfilm orientation.

There are other problems often encountered during the extrusion ofthermoplastic polymers. They include a build-up of the polymer at theorifice of the die (known as die build up or die drool), increase inback pressure during extrusion runs, and excessive degradation or lowmelt strength of the polymer due to high extrusion temperatures. Theseproblems slow the extrusion process either because the process must bestopped to clean the equipment or because the process must be run at alower speed.

Certain branched processing aids are known to partially alleviate meltdefects in extrudable thermoplastic hydrocarbon polymers and allow forfaster, more efficient extrusion.

U.S. Pat. No. 7,375,157 (Amos et al.) describes the use of afluoropolymer having long chain branching for use as a polymer meltadditive. The fluoropolymers are derived from bisolefins or halogenatedolefins, which comprise a halogen that is readily abstracted during thepolymerization, such as bromine or iodine.

U.S. Pat. Publ. No. 2010/0311906 (Lavallee et al.) also describes theuse of a fluoropolymer having long chain branching for use as a polymermelt additive. The fluoropolymers are derived from a fluorinated olefinmonomer and a fluorinated bisolefinic ether.

SUMMARY

Despite the many existing processing aids based on fluoropolymers asknown in the art, there continues to be a need to find furtherprocessing aids. The present disclosure is related to an alternativelong chain branched polymer that may be used as a processing aid inmelt-processible polymers. Desirably, such processing aids are highlyeffective in reducing melt defects in the processing, in particularextrusion, of non-fluorinated melt-processible polymers. Preferably, theprocessing aid is capable of reducing die drool and/or reducing the backpressure during extrusion of the non-fluorinated polymer.

In one aspect, a melt-processible polymer composition is providedcomprising:

a non-fluorinated melt-processible polymer; and

a fluorine-containing polymer derived from the polymerization of amonomer and a sulfinate-containing molecule, wherein thesulfinate-containing molecule is selected from the group consisting of:

wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; R is alinking group; Z₁ and Z₂ are independently selected from F, CF₃, and aperfluoroalkyl group; R₁ and R₂ are end-groups; p is 0 or 1; m is atleast 2; and M is a cation.

In another aspect, a melt-processible polymer composition is providedcomprising:

a non-fluorinated melt-processible polymer; and

a polymer comprising an end-group having a structures from groupconsisting of:

and combinations thereof;wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; R₇ is alinking group comprising at least 2 or more catenary atoms; and Z₁ andZ₂ are independently selected from F, CF₃, and a perfluoroalkyl group.

In another aspect, a polymer melt additive composition for use as aprocessing aid in the extrusion of a non-fluorinated polymer isprovided, the polymer melt additive composition comprising afluorine-containing polymer derived from the polymerization of a monomerand a sulfinate-containing molecule, wherein the sulfinate-containingmolecule is selected from the group consisting of:

wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; R is alinking group; Z₁ and Z₂ are independently selected from F, CF₃, and aperfluoroalkyl group; R₁ and R₂ are end-groups; p is 0 or 1; m is atleast 2; and M is a cation.

The above summary is not intended to describe each embodiment. Thedetails of one or more embodiments of the invention are also set forthin the description below. Other features, objects, and advantages willbe apparent from the description and from the claims.

DETAILED DESCRIPTION

As used herein, the term

“a”, “an”, and “the” are used interchangeably and mean one or more.

“and/or” is used to indicate one or both stated cases may occur, forexample A and/or B includes, (A and B) and (A or B).

“Oligomer” means less than 20,000 g/mol, less than 15,000 g/mol, lessthan 10,000 g/mol, less than 5,000 g/mol, less than 2,000 g/mol, lessthan 1,000 g/mol, and even less than 500 g/mol.

“Linking group” means a divalent linking group. In one embodiment, thelinking group includes at least 1 carbon atom (in some embodiments, atleast 2, 4, 8, 10, or even 20 carbon atoms). The linking group can be alinear or branched, cyclic or acyclic structure, that may be saturatedor unsaturated, substituted or unsubstituted, and optionally containsone or more hetero-atoms selected from the group consisting of sulfur,oxygen, and nitrogen, and/or optionally contains one or more functionalgroups selected from the group consisting of ester, amide, sulfonamide,carbonyl, carbonate, urethane, urea, and carbamate. In anotherembodiment, the linking group does not comprise a carbon atom and is acatenary heteroatom such as oxygen, sulfur, or nitrogen.

“Melt-processible” or “suitable for melt-processing” is meant that therespective polymer or composition can be processed in commonly usedmelt-processing equipment such as, for example, an extruder. Forexample, a melt processible polymer may typically have a melt flow indexof 5 g/10 minutes or less, preferably 2 g/10 minutes or less (measuredaccording to ASTM D1238 at 190 C, using a 2160 g weight) but still morethan 0.2 g/10 minutes. A melt-processible polymer may also have a meltflow index (MFI 265/5) of 20 g/10 minutes or less or 12 g/min or lessbut greater than 0.1 g/10 min.

“Sulfinate” is used to indicate both sulfinic acids and sulfinic acidsalts.

Also herein, recitation of ranges by endpoints includes all numberssubsumed within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75,9.98, etc.).

Also herein, recitation of “at least one” includes all numbers of oneand greater (e.g., at least 2, at least 4, at least 6, at least 8, atleast 10, at least 25, at least 50, at least 100, etc.).

Fluorine-Containing Polymers

Recently, unique monomers and oligomers comprising pendent sulfinicacids and salts thereof have been discovered. See U.S. Prov. Appl. Nos.61/492,885, 61/424,138, 61/424,109, 61/424,107, 61/424,146, and61/424,153, all filed on 17 Dec. 2011 and all herein incorporated byreference. The present disclosure is directed toward a compositioncomprising a fluorine-containing polymer derived from the polymerizationof a monomer and a sulfinate-containing molecule.

The sulfinate-containing molecule is selected from the group consistingof:

wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; R is alinking group; Z₁ and Z₂ are independently selected from F, CF₃, and aperfluoroalkyl group; R₁ and R₂ are end-groups; p is 0 or 1; m is atleast 2; and M is a cation.

In one embodiment R may be non-fluorinated, partially fluorinated, orperfluorinated. In some embodiments, the hydrogen atom in R may bereplaced with a halogen other than fluorine, such as a chlorine. R mayor may not comprise double bonds. R may be substituted or unsubstituted,linear or branched, cyclic or acyclic, and may optionally comprise afunctional group (e.g., esters, ethers, ketones, amines, halides, etc.).In one embodiment, R is a catenary heteroatom such as oxygen, sulfur, ornitrogen.

R₁ and R₂ are end-groups generated during oligomerization. Theseend-groups are independently selected from hydrogen, iodine, bromine,chlorine, a linear or branched alkyl, and a linear or branchedfluoroalkyl group, optionally containing catenary heteroatoms. In someembodiments, the alkyl or fluoroalkyl group has up to 20 carbon atoms.These end-groups are determined based on the initiator or chain transferagent and reaction conditions used to form the oligomer. For example,when a nonfluorinated initiator is used, hydrogen atoms may be presentas R₁ and R₂ in Formula (II). In one embodiment, R₁ and R₂ areperfluorinated such as when a perfluorinated initiator is used.

As used herein M represents a cation. Exemplary cations useful in thepresent disclosure include H⁺, NH₄ ⁺, PH₄ ⁺, H₃O⁺, Na⁺, Li⁺, Cs⁺, Ca⁺²,K⁺, Mg⁺², Zn⁺², and Cu⁺², and/or an organic cation including, but notlimited to N(CH₃)₄ ⁺, NH₂(CH₃)₂ ⁺, N(CH₂CH₃)₄ ⁺, NH(CH₂CH₃)₃ ⁺, NH(CH₃)₃⁺, ((CH₃CH₂CH₂CH₂)₄)P⁺, and combinations thereof.

Formula (II) as disclosed herein is an oligomer, meaning that Formula(II) has a number average molecular weight of no more than 20,000grams/mole, 15,000 grams/mole, 10,000 grams/mole, 5,000 grams/mole,2,000 grams/mole, 1000 grams/mol, or even 500 grams/mole. In oneembodiment, m is at least 1, 2, 3, 4, 6, 8, 10, or even at least 15.

In one embodiment, the sulfinate-containing molecule of Formulas (I) or(II), R is selected from: —(CH₂)_(a)—, —(CF₂)_(a)—, —O—(CF₂)_(a)—,—(CF₂)_(a)—O—(CF₂)_(b)—, —O(CF₂)_(a)—O—(CF₂)_(b)—,—(CF₂)_(a)—[O—(CF₂)_(b)]_(c)—, —O(CF₂)_(a)—[O—(CF₂)_(b)]_(c)—,—[(CF₂)_(a)—O]_(b) [(CF₂)_(c)—O]_(d)—,—O[(CF₂)_(a)—O]_(b)—[(CF₂)_(c)—O]_(d)—, —O—[CF₂CF(CF₃)O]_(a)—(CF₂)_(b)—,and combinations thereof, wherein a, b, c, and d are independently atleast 1, 2, 3, 4, 10, 20, etc.

In one embodiment, the sulfinate-containing molecule of Formula (I) isselected from the group consisting of: CF₂═CF—O(CF₂)_(n)—SO₂M;CF₂═CF—O[CF₂CF(CF₃)O]_(n)(CF₂)_(o)—SO₂M; CH₂═CH—(CF₂)_(n)—SO₂M; andcombinations thereof, where n is at least 1; o is at least 1; and M is acation.

In one embodiment, the sulfinate-containing molecule of Formula (II)comprises a segment selected from the group consisting of:

and combinations thereof, where n is at least 1; m is at least 1; o isat least 1, and M is a cation.

The oligomers and monomers of the present disclosure can be made usingmethods as disclosed in U.S. Prov. Appl. Nos. 61/492,885, 61/424,138,61/424,109, 61/424,107, 61/424,146, and 61/424,153, all filed Dec. 17,2010, all herein incorporated by reference.

In the present disclosure, a fluorine-containing polymer is derived fromthe polymerization of a monomer and a sulfinate-containing molecule. Themonomer is ethylenically unsaturated and can be selected fromnon-fluorinated, partially fluorinated, fully fluorinated monomers, andcombinations thereof.

In one embodiment, the monomer is selected from: dienes (includingnonfluorianted, partially fluorinated and perfluorinated dienes, forexample CH₂═CHR_(f)CH═CH₂, wherein Rf is a perfluorinated alkylenegroup, which may comprise 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 carbonatoms for example), halogenated alkenes, a fluoroalkyl substitutedethylene, allyl iodide, fluorinated alkyl vinyl ethers, fluorinatedalkoxy vinyl ethers, olefins, acrylates, styrene, vinyl ethers, andcombinations thereof.

Exemplary monomers include: tetrafluoroethylene, hexafluoropropylene,trifluoroethylene, vinylidene fluoride, vinyl fluoride,bromotrifluoroethylene, chlorotrifluoroethylene, CF₃CH═CF₂, C₄F₉CH═CH₂,CF₂═CHBr, CH₂═CHCH₂Br, CF₂═CFCF₂Br, CH₂═CHCF₂CF₂Br, CH₂═CHI, CF₂═CHI,CF₂═CFI, CH₂═CHCH₂I, CF₂═CFCF₂I, CH₂═CHCF₂CF₂I, CF₂═CFCH₂CH₂I,CF₂═CFCF₂CF₂I, CH₂═CH(CF₂)₆CH₂CH₂I, CF₂═CFOCF₂CF₂I, CF₂═CFOCF₂CF₂CF₂I,CF₂═CFOCF₂CF₂CH₂I, CF₂═CFCF₂OCH₂CH₂I, CF2=CFO(CF2)3-OCF2 CF2, CH2=CHBrand others as is known in the art.

In the present disclosure, the oligomers or monomers comprising thesulfinic acid or salt thereof, may be used in polymerization reactionsof polymers. Although not wanting to be bound by theory, it is believedthat the fluorinated sulfinate anion (RfSO₂ ⁻), acting as an electrondonor to form a fluorinated radical (Rf) by a single electron transfer(SET) to an oxidizing agent or electron acceptor to generate Rf—SO₂′following SO₂-elimination. Thus, the sulfinated compounds may act as aninitiator in radical polymerization reactions and theoretically beconsumed and incorporated into the polymer chain during thepolymerization. Although not wanting to be bound by theory, it is alsobelieved that because of the fast SET reaction of the fluorinatedsulfinate anion with a strong oxidizing agent or a strong electronacceptor, such as (NH₄)₂S₂O₈ to form a fluorinated radical, polymersmade using these initiator compounds may have reduced or no polarend-groups generated from the oxidizing agent, which may aid instability of the resulting polymer. The application of the combinedfluorinated sulfinate with an oxidation agent as co-initiator has beendemonstrated, such as in U.S. Pat. No. 5,285,002 (Grootaert).

The sulfinate-containing molecules as disclosed herein may also impartbranching of the polymer during polymerization. In one embodiment, thesulfinate-containing molecule of Formula (I) comprises both a doublebond and a sulfinate functional group, both of which can react underfree radical polymerization, the vinyl group acting as any traditionalvinyl group would react and the sulfinate group as described above. Inanother embodiment, the sulfinate-containing molecule (e.g., anoligomer) of Formula (II) comprises multiple sulfinate residues, each ofwhich is capable of forming a branch chain after generating the radicalspecies.

The level of branching or non-linearity can be characterized through thelong chain branching index (LCBI). The LCBI can be determined asdescribed in R. N. Shroff, H. Mavridis; Macromol., 32, 8464-8464 (1999)& 34, 7362-7367 (2001) according to the equation:

$\begin{matrix}{{LCBI} = {{\frac{\eta_{0,{{br}.}}^{1/a}}{\lbrack\eta\rbrack_{{br}.}} \cdot \frac{1}{k^{1/a}}} - 1}} & {{eq}.\mspace{14mu} 1}\end{matrix}$

In the above equation, η_(0,br) is the zero shear viscosity (units Pa s)of the branched polymer measured at a temperature T and [η]_(br) is theintrinsic viscosity (units ml/g) of the branched polymer at atemperature T′ in a solvent in which the branched polymer can bedissolved and a and k are constants. These constants are determined fromthe following equation:η_(0,lin) =k·[η] _(lin.) ^(a)  eq. 2wherein η_(0,lin) and [η]_(lin) represent respectively the zero shearviscosity and intrinsic viscosity of the corresponding linear polymermeasured at the respective same temperatures T and T′ and in the samesolvent. Thus, the LCBI is independent of the selection of themeasurement temperatures and solvent chosen provided of course that thesame solvent and temperatures are used in equations 1 and 2.

Generally, the effectiveness of the fluorine-containing polymer todecrease melt defects will increase with an increasing value of the LCBIfor polymers having similar zero shear rate viscosities (η₀). However,when the level of branching becomes too large, the polymer may have agel fraction that cannot be dissolved in an organic solvent and the LCBIvalue cannot be measured accurately since the measurement is based on asoluble solution. At such high levels of branching, the advantageouseffects of the fluorine-containing polymer on the processing of themelt-processible polymer composition are reduced as the melt viscosityof the fluoropolymer is too high. One skilled in the art through routineexperimentation may readily determine the appropriate value of LCBI.Generally, the LCBI will be between 0.2 and 5, preferably between 0.5and 1.5. In one embodiment, the LCBI is greater than 0.2, 0.5, 1, 1.5,2, 2.5, 4, or even 6.

In one embodiment of the present disclosure, the fluorine-containingpolymer of the present disclosure comprise a higher LCBI value, than thesame polymer prepared with an alternate branching agent, such as ahalogenated olefin.

The moieties of X₁, X₂, and X₃ and R and the selection of the monomerwill determine the fluorination (i.e., perfluorinated or partiallyfluorinated) of the fluorine-containing polymer. In one embodiment, thefluorine-containing polymer of the present disclosure areperfluorinated. In other words, all of the C—H bonds in the polymer arereplaced by C—F bonds, although the end groups may or may not befluorinated. In one embodiment, the polymers of the present disclosureare highly fluorinated, meaning that 80%, 90%, 95%, or even 99% of theC—H bonds in the polymer are replaced by C—F bonds. In anotherembodiment, the polymers of the present disclosure are partiallyfluorinated, meaning the polymer (excluding the end groups) comprises aleast one C—H bond.

The resulting fluorine-containing polymers of the present disclosure maybe amorphous, i.e., they have no melting point or hardly show a meltingpoint; semicrystalline, i.e., polymers that have a clearly detectablemelting point; or even crystalline.

The fluorine-containing polymers of the present disclosure aremelt-processible. This means the fluorine-containing polymers have anappropriate melt-viscosity that they can be melt-extruded at thetemperatures applied for melt-processing the non-fluorinated polymers.Melt processing typically is performed at a temperature from 180° C. to280° C., although optimum operating temperatures are selected dependingupon the melting point, melt viscosity, and thermal stability of thepolymer and also the type of extruder used.

The sulfinate-containing molecules should generally be used at fairlylow levels to avoid extensive branching during the polymerization. Theamount of sulfinate-containing molecules that is typically used in thepolymerization to cause a desired amount of branching of thefluorine-containing polymer depends on the sulfinate-containing moleculeused and on the polymerization conditions such as e.g., reaction time,temperature, and timing of the addition of the sulfinate-containingmolecule. The amount of sulfinate-containing molecule to be used isselected such that the desired LCBI value is attained. The optimalamount of sulfinate-containing molecules can be readily determined byone skilled in the art, but is generally not more than 4% by weight. Inone embodiment, at least 0.05, 0.1, 0.2, 0.3, 0.4, or even 0.5; and notmore than 2, 2.5, 3, 3.5, 4, 4.5, or even 5% by weight used based on thetotal weight of monomers fed to the polymerization.

Preparation of the Fluorine-Containing Polymer

The fluorine-containing polymers can be obtained with any of the knownpolymerization techniques including solution polymerization, suspensionpolymerization and polymerization in super critical CO₂. The polymersare preferably made through an aqueous emulsion polymerization process,which can be conducted in a known manner including batch, semi-batch, orcontinuous polymerization techniques. The reactor vessel for use in theaqueous emulsion polymerization process is typically a pressurizablevessel capable of withstanding the internal pressures during thepolymerization reaction. Typically, the reaction vessel will include amechanical agitator, which will produce thorough mixing of the reactorcontents and heat exchange system.

Any quantity of the monomer(s) and the sulfinate-containing moleculesmay be charged to the reactor vessel. The monomers and/or thesulfinate-containing molecules may be charged batchwise or in acontinuous or semicontinuous manner. By semi-continuous is meant that aplurality of batches of the monomer and/or and the sulfinate-containingmolecules are charged to the vessel during the course of thepolymerization. The independent rate at which the monomers and/or thesulfinate-containing molecules are added to the kettle, will depend onthe consumption rate with time of the particular monomer and/or thesulfinate-containing molecule. Preferably, the rate of addition ofmonomer and/or the sulfinate-containing molecules will equal the rate ofconsumption of monomer, i.e., conversion of monomer into polymer, and/orthe sulfinate-containing molecules.

The reaction kettle is charged with water. To the aqueous phase there isgenerally also added a fluorinated surfactant, typically a non-telogenicfluorinated surfactant although aqueous emulsion polymerization withoutthe addition of fluorinated surfactant may also be practiced. When used,the fluorinated surfactant is typically used in amount of 0.01% byweight to 1% by weight. Suitable fluorinated surfactants include anyfluorinated surfactant commonly employed in aqueous emulsionpolymerization. Particularly preferred fluorinated surfactants are thosethat correspond to the general formula:Y—R_(f)—Z-Mwherein Y represents hydrogen, Cl or F; R_(f) represents a linear orbranched perfluorinated alkylene having 4 to 10 carbon atoms; Zrepresents COO⁻ or SO₃ ⁻ and M represents an alkali metal ion or anammonium ion. Exemplary emulsifiers include: ammonium salts ofperfluorinated alkanoic acids, such as perfluorooctanoic acid andperfluorooctane sulphonic acid.

Also contemplated for use in the preparation of the polymers describedherein are emulsifiers of the general formula:[R_(f)—O-L-COO⁻]_(i)X_(i) ⁺  (VI)wherein L represents a linear partially or fully fluorinated alkylenegroup or an aliphatic hydrocarbon group, R_(f) represents a linearpartially or fully fluorinated aliphatic group or a linear partially orfully fluorinated group interrupted with one or more oxygen atoms, X_(i)⁺ represents a cation having the valence i and i is 1, 2 and 3. Specificexamples are described in, for example, US Pat. Publ. 2007/0015937(Hintzer et al.). Exemplary emulsifiers include: CF₃CF₂OCF₂CF₂OCF₂COOH,CHF₂(CF₂)₅COOH, CF₃(CF₂)₆COOH, CF₃O(CF₂)₃OCF(CF₃)COOH,CF₃CF₂CH₂OCF₂CH₂OCF₂COOH, CF₃O(CF₂)₃OCHFCF₂COOH, CF₃O(CF₂)₃OCF₂COOH,CF₃(CF₂)₃(CH₂CF₂)₂CF₂CF₂CF₂COOH, CF₃(CF₂)₂CH₂(CF₂)₂COOH, CF₃(CF₂)₂COOH,CF₃(CF₂)₂(OCF(CF₃)CF₂)OCF(CF₃)COOH, CF₃(CF₂)₂(OCF₂CF₂)₄OCF(CF₃)COOH,CF₃CF₂O(CF₂CF₂O)₃CF₂COOH, and their salts. In one embodiment, themolecular weight of the emulsifier is less than 1500, 1000, or even 500grams/mole.

These emulsifiers may be used alone or in combination as a mixture oftwo or more of them. The amount of the emulsifier is well below thecritical micelle concentration, generally within a range of from 250 to5,000 ppm (parts per million), preferably 250 to 2000 ppm, morepreferably 300 to 1000 ppm, based on the mass of water to be used.

A chain transfer agent may be used to control the molecular weight ofthe polymer so as to obtain the desired zero shear rate viscosity.Useful chain transfer agents include C₂-C₆ hydrocarbons such as ethane,alcohols, ethers, esters including aliphatic carboxylic acid esters andmalonic esters, ketones and halocarbons. Particularly useful chaintransfer agents are dialkylethers such as dimethyl ether and methyltertiary butyl ether.

In one embodiment, the polymerization is initiated after an initialcharge of the monomer and/or the sulfinate-containing molecule by addingan initiator or initiator system to the aqueous phase. For example,peroxides can be used as free radical initiators. Specific examples ofperoxide initiators include, hydrogen peroxide, diacylperoxides such asdiacetylperoxide, dipropionylperoxide, dibutyrylperoxide,dibenzoylperoxide, benzoylacetylperoxide, diglutaric acid peroxide anddilaurylperoxide, and further water soluble per-acids and water solublesalts thereof such as e.g. ammonium, sodium or potassium salts. Examplesof per-acids include peracetic acid. Esters of the peracid can be usedas well and examples thereof include tert-butylperoxyacetate andtert-butylperoxypivalate. A further class of initiators that can be usedare water soluble azo-compounds. Suitable redox systems for use asinitiators include for example a combination of peroxodisulphate andhydrogen sulphite or disulphite, a combination of thiosulphate andperoxodisulphate or a combination of peroxodisulphate and hydrazine.Exemplary persulphates include: sodium peroxodisulphates, potassiumperoxodisulphates, ammonium peroxodisulphates.

In yet another embodiment, a second fluoroalkyl sulfinates can be usedin conjection with oxidizing agents to initiate the polymerization.Exemplary second fluoroalkyl sulfinates include: C₄F₉SO₂M, wherein M isa cation. Further initiators that can be used are ammonium-alkali- orearth alkali salts of persulfates, permanganic or manganic acid ormanganic acids. The amount of initiator employed is typically between0.03 and 2% by weight, preferably between 0.05 and 1% by weight based onthe total weight of the polymerization mixture. The full amount ofinitiator may be added at the start of the polymerization or theinitiator can be added to the polymerization in a continuous way duringthe polymerization until a conversion of 70 to 80%. One can also addpart of the initiator at the start and the remainder in one or separateadditional portions during the polymerization. Accelerators such as forexample water-soluble salts of iron, copper and silver may also beadded.

During the initiation of the polymerization reaction, the sealed reactorkettle and its contents are conveniently pre-heated to the reactiontemperature. Polymerization temperatures are from 20° C. to 150° C.,preferred from 30° C. to 110° C. and most preferred from 40° C. to 100°C. The polymerization pressure is typically between 4 and 30 bar, inparticular 8 to 20 bar. The aqueous emulsion polymerization system mayfurther comprise auxiliaries, such as buffers and complex-formers.

The amount of polymer solids that can be obtained at the end of thepolymerization is typically between 10% and 45% by weight, preferablybetween 20% and 40% by weight and the average particle size of theresulting fluoropolymer is typically between 50 nm and 500 nm. Duringwork-up these particles sizes may be further increased to the finalparticle sizes by standard techniques (such as, e.g., agglomeration ormelt-pelletizing).

In one embodiment, the polymer comprises an end-group according toformulas III and IV may be obtained, wherein the end-group has astructures of:

and combinations thereof;wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; and Z₁ andZ₂ are independently selected from F, CF₃, and a perfluoroalkyl group.R₇ is a linking group that can be a linear or branched, cyclic oracyclic structure, that may be saturated or unsaturated, substituted orunsubstituted, and optionally contains one or more hetero-atoms selectedfrom the group consisting of sulfur, oxygen, and nitrogen, and/oroptionally contains one or more functional groups selected from thegroup consisting of ester, amide, sulfonamide, carbonyl, carbonate,urethane, urea, and carbamate. R₇ comprises at least 2 or more catenaryatoms so that at a minimum a 5-membered ring is achieved. As used hereinthe asterisk (*) is used to designate a polymer chain.

In one embodiment, these end-groups of Formula (III) and/or (IV) canoriginate from the intramolecular cyclization of thesulfinate-containing molecule, for example the vinyl sulfinated monomersof Formula (I).

Exemplary endgroups include:

However, other end-groups derived from the sulfinate-containing moleculemay be contemplated. See PCT Pat. Appl. No. US 2011/065339 (filed 16Dec. 2011, herein incorporated by reference).

In one embodiment, the polymer comprising an end-group according toformulas III and IV may further comprise interpolymerized units of amonomer. Such monomers may be selected from: dienes (includingnonfluorianted, partially fluorinated and perfluorinated dienes, forexample CH₂═CHR_(f)CH═CH₂, wherein Rf is a perfluorinated alkylenegroup, which may comprise 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 carbonatoms for example), halogenated alkenes, a fluoroalkyl substitutedethylene, allyl iodide, fluorinated alkyl vinyl ethers, fluorinatedalkoxy vinyl ethers, olefins, acrylates, styrene, vinyl ethers, andcombinations thereof.

Exemplary monomers include: tetrafluoroethylene, hexafluoropropylene,trifluoroethylene, vinylidene fluoride, vinyl fluoride,bromotrifluoroethylene, chlorotrifluoroethylene, CF₃CH═CF₂, C₄F₉CH═CH₂,CF₂═CHBr, CH₂═CHCH₂Br, CF₂═CFCF₂Br, CH₂═CHCF₂CF₂Br, CH₂═CHI, CF₂═CHI,CF₂═CFI, CH₂═CHCH₂I, CF₂═CFCF₂I, CH₂═CHCF₂CF₂I, CF₂═CFCH₂CH₂I,CF₂═CFCF₂CF₂I, CH₂═CH(CF₂)₆CH₂CH₂I, CF₂═CFOCF₂CF₂I, CF₂═CFOCF₂CF₂CF₂I,CF₂═CFOCF₂CF₂CH₂I, CF₂═CFCF₂OCH₂CH₂I, CF2=CFO(CF2)3-OCF2 CF2, CH2=CHBrand others as is known in the art.

Fluorine-Containing Polymer Compositions

The fluorine-containing polymers provided herein may be used asprocessing aids for facilitating or improving the quality of theextrusion of non-fluorinated polymers. They can be mixed withnon-fluorinated polymers during extrusion into polymer articles. Theycan also be provided as polymer compositions, so-called master batches,which may contain further components and/or one or more host polymers.Typically master batches contain the fluorine-containing polymerdispersed in or blended with a host polymer, which typically is anon-fluorinated polymer. Masterbatches may also contain furtheringredients, such as synergists, lubricants, etc. The masterbatch may bea composition ready to be added to a non-fluorinated polymer for beingextruded into a polymer article. The mater batch may also be acomposition that is ready for being directly processed into a polymerarticles without any further addition of non-fluorinated polymer.

The fluorine-containing polymer can be melt-processed (e.g., meltextruded) at the temperatures applied. Melt-processing typically isperformed at temperatures from 180° C. to 280° C., although optimumoperating temperatures are selected depending upon the melting point,melt viscosity, and thermal stability of the composition and also thetype of melt-processing equipment used. Generally, the composition mayhave a melt-flow index (measured according to ASTM D1238 at 190° C.,using 2160 g weight) of 5.0 g/10 minutes or less, preferably 2.0 g/10minutes or less. Generally the melt flow indexes are greater than 0.1 orgreater than 0.2 g/10 min.

Such composition may be further mixed with further non-fluorinatedpolymer and/or further components to obtain a composition ready forprocessing into a polymer article. The composition may also contain allrequired ingredients and are ready for being extruded into a polymerarticle. The amount of the fluorine-containing polymer in thesecompositions is typically relatively low. The exact amount used may bevaried depending upon whether the extrudable composition is to beextruded into its final form (e.g. a film) or whether it is to be usedas a master batch or processing additive which is to be (further)diluted with additional host polymer before being extruded into itsfinal form.

Generally, the fluorine-containing polymer composition comprises fromabout 0.002 to 50 weight % of the fluorine-containing polymer. If thefluorine-containing polymer composition is a master batch or processingadditive, the amount of fluoropolymer may vary between about 1 to 50weight % of the composition. If the fluorine-containing polymercomposition is to be extruded into final form and is not further dilutedby the addition of host polymer, it typically contains a lowerconcentration of the fluorine-containing polymer, e.g., about 0.002 to 2wt %, and preferably about 0.005 ns 0.2 wt % of the fluorine-containingpolymer composition. In any event, the upper concentration of thefluorine-containing polymer used is generally determined by economiclimitations rather than by adverse physical effects of the concentrationof the fluorine-containing polymer composition.

In one embodiment, the composition may comprise blends offluorine-containing polymers which comprise different MFIs, Mooneyviscosity, and/or LCBIs. See for example, U.S. Pat. No. 6,277,919(Dillon et al.).

In another embodiment the composition may comprise a second polymerprocessing additive as is known in the art, such as a fluoropolymerobtained from a bisolefin, a fluoropolymer obtained from a halogenatedolefin, siloxanes, etc.

The fluorine-containing polymer composition may be used in the form of apowder, pellet, granule of a desired particulate size or sizedistribution, or any other extrudable form.

The fluorine-containing polymer compositions may comprisefluorine-containing polymers having average particle sizes (weightaverage) of greater than about 50 nm, or greater than about 500 nm orgreater than about 2 μm or even greater than about 10 μm. In a typicalembodiment, the fluorine-containing polymer may have an average particlesize (weight average) of from about 1 to about 30 μm.

Non-Fluorinated Polymers (Host Polymers)

A wide variety of non-fluorinated polymers are useful as host polymers.The non-fluorinated melt processible polymers may be selected from avariety of polymer types. Host polymers include, but are not limited to,hydrocarbon resins, polyamides (including but not limited to nylon 6,nylon 6/6, nylon 6/10, nylon 11 and nylon 12), polyester (including butnot limited to poly (ethylene terephthalate) and poly (butyleneterephthalate)), chlorinated polyethylene, polyvinyl resins such aspolyvinylchloride, polyacrylates and polymethylacrylates,polycarbonates, polyketones, polyureas, polyimides, polyurethanes,polyolefins and polystyrenes.

The non-fluorinated polymers host polymers are melt-processible.Typically, the polymers, including hydrocarbon polymers, have melt flowindexes (measured according to ASTM D1238 at 190° C., using a 2160 gweight) of 5.0 g/10 minutes or less, preferably 2.0 g/10 minutes.Generally the melt flow indexes are greater than 0.1 or 0.2 g/10 min.

A particularly useful class of host polymers are hydrocarbon polymers,in particular, polyolefins. Representative examples of usefulpolyolefins are polyethylene, polypropylene, poly (1-butene), poly(3-methylbutene), poly (4-methylpentene) and copolymers of ethylene withpropylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene,and 1-octadecene.

Representative blends of useful polyolefins include blends ofpolyethylene and polypropylene, linear or branched low-densitypolyethylenes (e.g. those having a density of from 0.89 to 0.94 g/cm³),high-density polyethylenes (metallocene-catalyzed or notmetallocene-catalyzed), including those having a density of e.g. from0.94 to about 0.98 g/cm³, and polyethylene and olefin copolymerscontaining said copolymerizable monomers, some of which are describedbelow, e.g., ethylene and acrylic acid copolymers; ethylene and methylacrylate copolymers; ethylene and ethyl acrylate copolymers; ethyleneand vinyl acetate copolymers; ethylene, acrylic acid, and ethyl acrylatecopolymers; and ethylene, acrylic acid, and vinyl acetate copolymers.

The polyolefins may be obtained by the homopolymerization orcopolymerization of olefins, as well as copolymers of one or moreolefins and up to about 30 weight percent or more, but preferably 20weight percent or less, of one or more monomers that are copolymerizablewith such olefins, e.g. vinyl ester compounds such as vinyl acetate. Theolefins may be characterized by the general structure CH₂═CHR, wherein Ris a hydrogen or an alkyl radical, and generally, the alkyl radicalcontains not more than 10 carbon atoms, preferably from one to sixcarbon atoms. Representative olefins are ethylene, propylene, 1-butene,1-hexene, 4-methyl-1-pentene, and 1-octene. Representative monomers thatare copolymerizable with the olefins include: vinyl ester monomers suchas vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate,and vinyl chloropropionate; acrylic and alpha-alkyl acrylic acidmonomers and their alkyl esters, amides, and nitriles such as acrylicacid, methacrylic acid, ethacrylic acid, methyl acrylate, ethylacrylate, N,N-dimethyl acrylamide, methacrylamide, and acrylonitrile;vinyl aryl monomers such as styrene, o-methoxystyrene, p-methoxystyrene,and vinyl naphthalene; vinyl and vinylidene halide monomers such asvinyl chloride, vinylidene chloride, and vinylidene bromide; alkyl estermonomers of maleic and fumaric acid and anhydrides thereof such asdimethyl maleate, diethyl maleate, and maleic anhydride; vinyl alkylether monomers such as vinyl methyl ether, vinyl ethyl ether, vinylisobutyl ether, and 2-chloroethyl vinyl ether; vinyl pyridine monomers;N-vinyl carbazole monomers; and N-vinyl pyrrolidine monomers.

Useful host polymers also include the metallic salts of the olefincopolymers, or blends thereof, that contain free carboxylic acid groups.Illustrative of the metals that can be used to provide the salts of saidcarboxylic acids polymers are the one, two, and three valence metalssuch as sodium, lithium, potassium, calcium, magnesium, aluminum,barium, zinc, zirconium, beryllium, iron, nickel, and cobalt.

Useful host polymers also include blends of various thermoplasticpolymers and blends thereof containing conventional adjuvants such asantioxidants, light stabilizers, fillers, antiblocking agents, andpigments.

The host polymers may be used in the form of powders, pellets, granules,or in any other extrudable form. The most preferred olefin polymersuseful in the invention are hydrocarbon polymers such as homopolymers ofethylene and propylene or copolymers of ethylene and 1-butene, 1-hexene,1-octene, 4-methyl-1-pentene, propylene, vinyl acetate and methylacrylate. The melt processible composition of the present disclosure canbe prepared by any of a variety of ways. For example, the host polymerand the fluorine-containing polymer can be combined together by any ofthe blending means usually employed in the plastics industry, such aswith a compounding mill, a Banbury mixer, or a mixing extruder in whichthe fluoropolymer is uniformly distributed throughout the host polymer.The fluorine-containing polymer and the host polymer may be used in theform, for example, of a powder, a pellet, or a granular product. Themixing operation is most conveniently carried out at a temperature abovethe melting point or softening point of the fluoropolymer, though it isalso feasible to dry-blend the components in the solid state asparticulates and then cause uniform distribution of the components byfeeding the dry blend to a twin-screw melt extruder.

The resulting melt-blended mixture can be pelletized or otherwisecomminuted into a desired particulate size or size distribution and fedto an extruder, which typically will be a single-screw extruder, thatmelt-processes the blended mixture. Melt-processing typically isperformed at a temperature from 180° C. to 280° C., although optimumoperating temperatures are selected depending upon the melting point,melt viscosity, and thermal stability of the blend. Different types ofextruders that may be used to extrude the compositions of this inventionare described, for example, by Rauwendaal, C., “Polymer Extrusion”,Hansen Publishers, p. 23-48, 1986. The die design of an extruder canvary, depending on the desired extrudate to be fabricated. For example,an annular die can be used to extrude tubing, useful in making fuel linehose, such as that described in U.S. Pat. No. 5,284,184 (Noone et al.),which description is incorporated herein by reference.

The blended composition can contain conventional adjuvants such asantioxidants, antiblocks, pigments, and fillers, e.g. titanium dioxide,carbon black, and silica.

Antiblocks, when used, may be coated or uncoated materials. In oneembodiment, a synergist is added to the melt-processible composition. By‘synergist’ is meant a compound, generally non-fluorinated organiccompound, that allows the use of a lower amount of thefluorine-containing polymer while achieving essentially the sameimprovement in extrusion and processing properties of thenon-fluorinated polymer as if a higher amount of the fluorine-containingpolymer was used.

Exemplary synergists include: polyethylene glycol, polycaprolactone,silicone-polyethers, aliphatoic polyesters, aromatice polyesters, amineoxides, carboxylic acids, fatty acid esters, and combinations thereof.

The fluorine-containing polymer may also be combined with a poly(oxyalkylene) polymer component as a so-called synergist. The poly(oxyalkylene) polymer component may comprise one or more poly(oxyalkylene) polymers. A useful processing additive compositioncomprises between about 5 and 95 weight percent of the poly(oxyalkylene) polymer component and 95 and 5 weight percent of thefluorine-containing polymer. Typically, the ratio of thefluorine-containing polymer to the poly (oxyalkylene) polymer componentin the processing aid will be from 1/2 to 2/1.

The poly (oxyalkylene) polymer component generally may comprise betweenabout 0.002 and 20 weight percent of the overall melt processiblecomposition, more preferably between about 0.005 and 5 weight percent,and most preferably between about 0.01 and 1 weight percent. Generally,poly (oxyalkylene) polymers useful in this invention include poly(oxyalkylene) polyols and their derivatives. A class of such poly(oxyalkylene) polymers may be represented by the general formula:A[(OR³)_(x)OR²]_(y)wherein: A is an active hydrogen-free residue of a low molecular weight,initiator organic compound having a plurality of active hydrogen atoms(e.g, 2 or 3), such as a polyhydroxyalkane or a polyether polyol, e.g.,ethylene glycol, glycerol, 1,1,1-trimethylol propane, and poly(oxypropylene) glycol; y is 2 or 3; (OR³)_(x) is a poly (oxyalkylene)chain having a plurality of oxyalkylene groups, OR³ wherein the R³moieties can be the same or different and are selected from the groupconsisting of C₁ to C₅ alkylene radicals and, preferably, C₂ or C₃alkylene radicals, and x is the number of oxyalkylene units in saidchain. Said poly (oxyalkylene) chain can be a homopolymer chain, e.g.,poly (oxyethylene) or poly (oxypropylene), or can be a chain of randomlydistributed (i.e., a heteric mixture) oxyalkylene groups, e.g., acopolymer —OC₂H₄— and —OC₃H₆— units, or can be a chain havingalternating blocks or backbone segments of repeating oxyalkylene groups,e.g., a polymer comprising (—OC₂H₄—)_(a) and (—OC₃H₆—)_(b) blocks,wherein a+b=5 to 5000 or higher, and preferably 10 to 500.

R₂ is H or an organic radical, such as alkyl, aryl, or a combinationthereof such as aralkyl or alkaryl, and may contain oxygen or nitrogenheteroatoms. For example, R₂ can be methyl, butyl, phenyl, benzyl, andacyl groups such as acetyl, benzoyl and stearyl.

Representative poly (oxyalkylene) polymer derivatives can include poly(oxyalkylene) polyol derivatives wherein the terminal hydroxy groupshave been partly or fully converted to ether derivatives, e.g., methoxygroups, or ester derivatives, e.g., stearate groups. Other useful poly(oxyalkylene) derivatives are polyesters, e.g., prepared fromdicarboxylic acids and poly (oxyalkylene) glycols. Preferably, the majorproportion of the poly (oxyalkylene) polymer derivative by weight willbe the repeating oxyalkylene groups, (OR₃).

The poly (oxyalkylene) polyols and their derivatives can be those whichare solid at room temperature and have a molecular weight of at leastabout 200 and preferably a molecular weight of about 400 to 20,000 orhigher. Poly (oxyalkylene) polyols useful in this invention includepolyethylene glycols which can be represented by the formulaH(OC₂H₄)_(n)OH, where n is about 15 to 3000, such as those sold underthe trade designation “CARBOWAX”, such as “CARBOWAX PEG8000”, where n isabout 180, e.g. 181, and those sold under the trade name “POLYOX”, suchas “POLYOX WSR N-10” where n is about 2300, e.g. 2272.

As an alternative to or in combination with a poly (alkyleneoxy)polymer, there can also be used any of the following polymers assynergists: i) silicone-polyether copolymers; ii) aliphatic polyesterssuch as poly (butylene adipate), poly (lactic acid) and polycaprolactonepolyesters and iii) aromatic polyesters such as phthalic acid diisobutylester.

A preferred aliphatic polyester is a polycaprolactone having a numberaverage molecular weight in the range 1000 to 32000, preferably 2000 to10000, and most preferably 2000 to 4000.

The melt-processible compositions of the present disclosure may be usedin articles. In one embodiment, the fluorine-containing polymercomposition is useful in the extrusion of non-fluorinated polymers,which includes for example, extrusion of films, extrusion blow molding,injection molding, pipe, wire and cable extrusion, and fiber production.

Exemplary embodiments of the present disclosure include:

Item 1. A melt-processible polymer composition comprising: anon-fluorinated melt-processible polymer; and a fluorine-containingpolymer derived from the polymerization of a monomer and asulfinate-containing molecule, wherein the sulfinate-containing moleculeis selected from:

-   -   wherein X₁, X₂, and X₃ are each independently selected from H,        F, Cl, a C₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl        group; R is a linking group; Z₁ and Z₂ are independently        selected from F, CF₃, and a perfluoroalkyl group; R₁ and R₂ are        end-groups; p is 0 or 1; m is at least 2; and M is a cation.

Item 2. The melt-processible polymer composition of item 1, wherein thesulfinate-containing molecule of Formula (I) is selected from:CF₂═CF—O(CF₂)_(n)—SO₂M; CH₂═CH—(CF₂)_(n)—SO₂M;CF₂═CF—O[CF₂CF(CF₃)O]_(n)(CF₂)_(o)—SO₂M; and combinations thereof, wheren is at least 1, o is at least 1, and M is a cation.

Item 3. The melt-processible polymer composition of any one of theprevious items, wherein the sulfinate-containing molecule of Formula(II) comprises a segment selected from:

and combinations thereof, where n is at least 1, o is at least 1, and mis at least 1.

Item 4. The melt-processible polymer composition of any one of theprevious items, wherein the fluorine-containing polymer is furtherderived from a second fluoroalkyl sulfinate initiator.

Item 5. The melt-processible polymer composition of item 4, wherein thesecond fluoroalkyl sulfinate initiator is C₄F₉SO₂M, wherein M is acation.

Item 6. The melt-processible polymer composition of any one of theprevious items, wherein the monomer is selected from dienes, halogenatedalkenes, a fluoroalkyl substituted ethylene, allyl iodide, fluorinatedalkyl vinyl ethers, fluorinated alkoxy vinyl ethers, olefins, acrylates,styrene, vinyl ethers, and combinations thereof.

Item 7. The melt-processible polymer composition of any one of theprevious items, wherein the monomer is selected from:tetrafluoroethylene, hexafluoropropylene, trifluoroethylene vinylidenefluoride, vinyl fluoride, bromotrifluoroethylene,chlorotrifluoroethylene, CF₃CH═CF₂, C₄F₉CH═CH₂, CF₂═CHBr, CH₂═CHCH₂Br,CF₂═CFCF₂Br, CH₂═CHCF₂CF₂Br, and combinations thereof.

Item 8. The melt-processible polymer composition of any one of theprevious items, wherein the fluorine-containing polymer is crystalline.

Item 9. The melt-processible polymer composition of any one of items1-7, wherein the fluorine-containing polymer is semi-crystalline, oramorphous.

Item 10. The melt-processible polymer composition of any one of theprevious items, wherein the fluorine-containing polymer is partiallyfluorinated.

Item 11. The melt-processible polymer composition of any one of items1-9, wherein the fluorine-containing polymer is fully fluorinated.

Item 12. The melt-processible polymer composition of any one of theprevious items, wherein the fluorine-containing polymer has an LCBI ofgreater than 0.2.

Item 13. A melt-processible polymer composition comprising: anon-fluorinated melt-processible polymer; and a polymer comprising anend-group having a structures selected from:

and combinations thereof;wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; R₇ is alinking group comprising at least 2 or more catenary atoms; and Z₁ andZ₂ are independently selected from F, CF₃, and a perfluoroalkyl group.

Item 14. The melt-processible polymer composition of item 13, whereinthe end-group is selected from:

Item 15. The melt-processible polymer composition of any one of items 13to 14, further comprising interpolymerized units of a monomer, whereinthe monomer is selected from: dienes, halogenated alkenes, a fluoroalkylsubstituted ethylene, allyl iodide, fluorinated alkyl vinyl ethers,fluorinated alkoxy vinyl ethers, olefins, acrylates, styrene, vinylethers, and combinations thereof.

Item 16. The melt-processible polymer composition of item 15, whereinthe monomer is selected from: tetrafluoroethylene, hexafluoropropylene,trifluoroethylene, vinylidene fluoride, vinyl fluoride,bromotrifluoroethylene, chlorotrifluoroethylene, CF₃CH═CF₂, C₄F₉CH═CH₂,CF₂═CHBr, CH₂═CHCH₂Br, CF₂═CFCF₂Br, CH₂═CHCF₂CF₂Br, and combinationsthereof.

Item 17. The melt-processible polymer composition of any one of theprevious items, further comprising a synergist.

Item 18. The melt-processible polymer composition of item 14, whereinthe synergist is polyethylene glycol or polycaprolactone.

Item 19. An article comprising the melt-processible polymer compositionof any one of the previous items.

Item 20. A polymer melt additive composition for use as a processing aidin the extrusion of a non-fluorinated polymer, the polymer melt additivecomposition comprising a fluorine-containing polymer derived from thepolymerization of a monomer and a sulfinate-containing molecule, whereinthe sulfinate-containing molecule is selected from:

wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; R is alinking group; Z₁ and Z₂ are independently selected from F, CF₃, and aperfluoroalkyl group; R₁ and R₂ are end-groups; p is 0 or 1; m is atleast 2; and M is a cation. Item 21. The polymer melt additivecomposition of item 20, wherein the polymer melt additive compositionwhen extruded with a non-fluorinated polymer, eliminates melt fracturein the non-fluorinated polymer at lower amounts than a comparativepolymer melt additive composition derived from the fluorine-containingpolymer that does not consist of the one or more modifiers.

Item 22. The polymer melt additive composition of any one of items17-21, further comprising a synergist.

Item 23. The polymer melt additive composition of item 22, wherein thesynergist is polyethylene glycol, polycaprolactone, or combinationsthereof.

EXAMPLES

Advantages and embodiments of this disclosure are further illustrated bythe following examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. In theseexamples, all percentages, proportions and ratios are by weight unlessotherwise indicated.

All materials are commercially available, for example from Sigma-AldrichChemical Company; Milwaukee, Wis., or known to those skilled in the artunless otherwise stated or apparent.

These abbreviations are used in the following examples: g=gram, hr=hour,kg=kilograms, min=minutes, cm=centimeter, mm=millimeter, ml=milliliter,dl=deciliter, l=liter, mol=moles, kPa=kilopascals, MPa=megapascals,FT-IR=Fouier Transform Infrared Spectroscopy, psi=pressure per squareinch, [η]=intrinsic viscosity, rad/s=radians/sec SI unit of angularvelocity, MV=Mooney Viscosity, MI=melt index in g/10 min @ 190° C. and2.6 kg weight, and wt=weight, LCBI=Long Chain Branching Index.

Material Characterization

The Mooney viscosity was determined according to ASTM D1646-06 Part A“Rubber-Viscosity, Stress Relaxation, and Pre-vulcanizationCharacteristics [Mooney viscometer]” by a MV 2000 instrument (availablefrom Alpha Technologies, Akron, Ohio) using large rotor (ML 1+10) at121° C. Results are reported in Mooney units.

Solution viscosities of diluted polymer solutions were determinedusually on a 0.25% wt (0.2 g/dl) polymer solution in methylethylketone(MEK) at 35° C. in accordance to ASTM D2857, and D 446. AConnon-Fenske-Routine-Viscosimeter (Fa. Schott, Mainz/Germany) was usedfor the measurements. The so obtained inherent or reduced viscositiesη_(red) were converted into the intrinsic viscosity [η] using theHuggins equation η_(red)=[η]+k_(H)×[η]²×c and a Huggins constant ofk_(H)=0.34. The intrinsic viscosity [η] as well as the reducedviscosity. η_(red) are reported in physical units of ml/g, the inherentviscosity (IV) is reported in physical units of dl/g.

The melt viscosity was measured using an AR2000ex parallel platerheometer from TA instruments. It was fitted with Nickel plated 25 mmdisposable plates mounted on an electrically heated plates system (EHP).The materials were pressed into a bubble free 1.25 mm sheet at 130° C.For each material, a 30 mm disc was cut out and placed between therheometer plates at 150° C. The gap was set at 1.1 mm and the sample wastrimmed after the normal force stabilized. The gap was then set to 1.0mm and the measurement was initialized after the normal forcestabilized.

The test procedure was a time and frequency sweep, with five points perdecade, at frequencies ranging from 0.1 to 398.1 rad/s, and at sixtemperatures, ranging from 150° C. to 250° C., and a strain of 10%.

The η′ and η* data was fitted simultaneously to the combinedCarreau-Yasuda model and Arrhenius equation, as described in U.S. Pat.No. 5,830,947 (Blong et al.), to obtain the zero shear viscosity.

The “Long Chain Branching Index” (LCBI) was calculated according to themethod described in U.S. Pat. No. 7,375,157 (Amos et al.).

Blown Film Evaluation Method

For evaluation in a blown film line, concentrates of Polymer ProcessingAdditive (PPA) were prepared at a level of 3% in a 2MI Linear LowDensity Polyethylene (LLDPE) which was stabilized with 1000 ofantioxidant and 700 ppm of acid neutralizer. The concentrates werecompounded using a “Haake Rheomix TW-100” counter-rotating,intermeshing, conical twin screw extruder (commercially available fromThermo Fischer Scientific, Waltham, Mass.). Prior to compounding, theresin, antioxidants and fluoropolymer additive were dry-blended in abag. This powder blend was starve-fed to the compounder at a nominalrate of 3.3 kg/hr. The extruder was operating at 150 rpm, with anextrusion profile of 170° C./190° C./200° C. and die temp of 200° C. Theextrudate was water quenched and the strand pelletized. The resultingpellets were collected in a plastic bag, hand mixed by shaking, andpassed through the extruder a second time by flood feeding with a screwspeed of 90 rpm to ensure adequate dispersion and distribution of thefluorine-containing polymer within the host resin.

Samples for extrusion were prepared by weighing the required amount ofpolymer processing additive concentrate, 0.9 MI LLDPE resin and otheradditive concentrates into a 5 gallon pail and mixing on a pail tumblerfor a minimum of 10 min.

Films were produced using a Kiefel blown film line (commerciallyavailable from Riefenhäuser GmbH, Troisdorf, Germany) with a 40 mm,24/1:L/D, grooved feed extruder. The die was of spiral design, with adiameter of 40 mm and a die gap of 0.9 mm. An adjustable single lip airring with chilled air was used for cooling. An iris and sizing cageprovided further bubble stability. Film was produced with a nominalgauge of 25 microns, with a lay flat width of approximately 22 cm.

The Kiefel temperature zones (two extruder, one adapter and three diezones) were set at 130° C. (feed), 195° C., 205° C., 210° C., 210° C.,210° C. respectively, where the die adapter zone was adjusted tomaintain a target melt temperature of 210° C. The screw was maintainedat about 35 rpm to deliver an output of about 10 kg/hr corresponding toa shear rate of about 220 s⁻¹.

Prior to each evaluation it was necessary to ensure that the blown filmline was free of residual fluorine-containing polymer from the previousevaluation. This was accomplished by gently cleaning the die with abrass brush and pad sold under the trade designation “SCOTCH-BRITE”available from 3M Co., St. Paul, Minn. A 50/50 (by volume) blend ofpurge compound and 0.9 ml LLDPE (approximately 20 kg) was used to purgethe extruder. The screw speed was gradually increased from 40 to 140rpm, this was followed by 20 kg of 0.9 MI LLDPE, while maintaining thepressure below 5000 psi. The base resin was then extruded into film,under the original conditions for a minimum of 30 min, until thepreviously determined extrusion pressure was achieved and the resultantfilm was fully melt fractured.

The percent melt fracture was determined by taking a section of the filmlay flat, opening it along the edge, measuring the individual bands(regions) of melt fracture in the transverse direction of the film,summing their total, and then dividing by the total width of the openedlay flat film.

MV4SO2H and MV4SO2NH4 Synthesis

50 g (0.13 mol) MV4S and 150 ml of reagent grade ethanol was added to a1 liter 3-neck round bottom flask. The solution was stirred and cooledto 0° C. 3.4 g (0.09 mol) NaBH₄ was added in portions over 30 minuteswith a 5° C. exothermic temperature rise per portion. The reaction waskept under 10° C. throughout the addition of NaBH₄. The flask wasallowed to warm to 20° C. and the slurry was stirred for 30 minutes. 26g concentrated H₂SO₄ in 200 g water was added slowly resulting in atemperature rise to 32° C. A lower fluorochemical phase of 31 g ofunreacted MV4S was recovered. The clear top solution was extracted with110 g methyl-t-butyl ether (MTBE) and vacuum stripped to recover 28 g ofa semi-solid material. The semi-solid material still contained somewater, ethanol, and salts. NMR gave the desired MV4SO₂H in an 86% yieldbased on reacted MV4S. The ammonium salt was made by titration withammonium hydroxide.

Synthesis of PPA1

An 80 l reactor was charged with 52 kg water, 112 g ammonium persulfate(APS, (NH₄)₂S₂O₈), 206 g 50% aqueous solution of potassium phosphatedibasic (K₂HPO₄) and 36.8 g diethylmalonate. The reactor was evacuated,the vacuum was broken and it was pressurized with nitrogen to 0.17 MPa.This vacuum and pressurization was repeated three times. After removingoxygen, the reactor was heated to 71.1° C. and the vacuum was broken andthen pressurized with hexafluoropropylene (HFP) to 0.28 MPa. The reactorwas then charged with vinylidene fluoride (VDF) and hexafluoropropylene(HFP), bringing reactor pressure to 1.03 MPa. Total precharges of VDFand HFP was 675 g and 894 g, respectively. The reactor was agitated at450 rpm. As reactor pressure dropped due to monomer consumption in thepolymerization reaction, HFP and VDF was continuously fed to the reactorto maintain the pressure at 1.03 MPa. The ratio of the blend to VDF was0.651 by weight and no emulsifier was used for the polymerization. After4 hrs the monomer and blend feeds were discontinued and the reactor wascooled. The resulting dispersion had a solid content of 30% by weightand a pH of 3.9. The dispersion particle size was 350 nm and totalamount of dispersion was about 74.3 kg.

For the coagulation, 942 g of the latex made as described above wasadded to 2,320 mL of a 1.25% MgCl₂ by weight in water solution. Thecrumb was recovered by filtering the coagulate through cheese cloth andgently squeezing to remove excess water. The crumb was returned to thecoagulation vessel and rinsed with deionized water a total of 3 times.After the final rinse and filtration, the crumb was dried in a 130° C.oven for 16 hrs. The resulting fluoropolymer raw gum had a Mooneyviscosity of 70 at 121° C.

Synthesis of FKM4

A 4 liter reactor was charged with 2.25 kg water, 1.7 g diethyl malonate(DEM), an aqueous solution containing 5.2 g ammonium persulfate (APS,(NH₄)₂S₂O₈), and 5.0 g potassium phosphate dibasic (K₂HPO₄). Containersfrom which the solid reagents were added were rinsed, and the rinsewater, totaling 350 g, was added to the reactor. The reactor wasevacuated; the vacuum was broken and the vessel was pressurized withnitrogen to 25 psi (0.17 MPa). This evacuation and pressurization cyclewas repeated three times. After removing oxygen, the reactor was heatedto 73.3° C. and pressurized with 22 g hexafluoropropylene (HFP). Thereactor was then charged with 139 g vinylidene fluoride (VDF) and 109grams of hexafluoropropylene (HFP). The reactor was agitated at 650 rpm.As reactor pressure dropped due to monomer consumption in thepolymerization reaction, HFP and VDF were continuously fed to thereactor to maintain the pressure at 160 psi (1.11 MPa). The ratio of HFPand VDF was 0.651 by weight. Concurrently, a 20% w/w solution ofMV4SO2NH4 vinyl sulfinate monomer (ammonium salt) was fed continuously,such that 15 grams of monomer (75 g solution) was fed over the course ofthe polymerization. After 750 grams of VDF had been introduced, themonomer feeds were discontinued and the reactor was cooled. Theresulting dispersion had a solid content of 31.1 wt % and a pH of 3.4.The mean particle size in the latex was 259 nm and the total amount ofdispersion was about 3,880 grams.

For the coagulation, 3000 g of the dispersion made as described abovewas added to 3,038 g of a 1.25 wt % aqueous solution of MgCl₂. The crumbwas recovered by filtering the coagulate through cheese cloth and gentlysqueezing to remove excess water. The crumb was returned to thecoagulation vessel and rinsed with deionized water a total of 4 times.After the final rinse and filtration, the crumb was dried in a 130° C.oven for 16 hrs. The resulting fluoroelastomer raw gum had a Mooneyviscosity of 55 at 121° C.

The fluoroelastomer by FT-IR analysis contained 79.7 mol % copolymerizedunits of VDF and 20.3 mol % HFP. The fluorine content was 65.6 wt %.

Synthesis of FKM5

An 80 liter reactor was charged with 51 kg water, 36.8 g diethylmalonate (DEM), an aqueous solution containing 112.9 g ammoniumpersulfate (APS, (NH₄)₂S₂O₈), and 103 g potassium phosphate dibasic(K₂HPO₄). Containers from which the solid reagents were added wererinsed, and the rinse water, totaling 500 g, was added to the reactor.The reactor was evacuated; the vacuum was broken and the vessel waspressurized with nitrogen to 25 psi (0.17 MPa). This evacuation andpressurization cycle was repeated three times. After removing oxygen,the reactor was heated to 73.8° C. and pressurized with 440 ghexafluoropropylene (HFP). The reactor was then charged with 2780 gvinylidene fluoride (VDF) and 2180 g of hexafluoropropylene (HFP). Thereactor was agitated at 450 rpm. As reactor pressure dropped due tomonomer consumption in the polymerization reaction, HFP and VDF werecontinuously fed to the reactor to maintain the pressure at 155 psi(1.11 MPa). The ratio of HFP and VDF was 0.651 by weight. After 14.884kg of VDF had been introduced, the monomer feeds were discontinued andthe reactor was cooled. The resulting dispersion had a solid content of31.9 wt % and a pH of 3.7. The mean particle size in the latex was 325nm. The coagulation was done according to the method described under“Synthesis of FKM4”.

Synthesis of CH₂═CH(CF₂)₃SO₂H

In a 600 mL PARR pressure reactor, 198.4 g (MW=404, 0.491 mol) I(CF₂)₃Iwas reacted with 15.4 g (MW=28, 0.55 mol) CH₂═CH₂ (charged in portions)in the presence of 4.58 g “VAZO-67” (E.I. du Pont de Nemours & Co,Wilmington, Del.) at 60° C. for 24 hrs under 60 psi (414 kPa) or less.Distillation afforded 95 g ICH₂CH₂CF₂CF₂CF₂I with a boiling point at54-62° C. 1 mm-Hg. From ¹⁹F NMR analysis, the NMR purity is ˜98% withsmall amount of unreacted I(CF₂)₃I and bis-adduct, I(CH2)2(CF2)3(CH2)2I(isolated yield: ˜44.8%). ¹⁹F NMR analysis confirmed the product: −58ppm (txt, 2F, —CF2I), −113 (txt, 2F), −114 (m, 2F); ¹H NMR ofICH₂CH₂CF₂CF₂CF₂I: 3.5 ppm (m, 2H), 3.0 (m, 2H, —CF2CH2-).

Under nitrogen, 43.5 g (MW=432, 0.1 mol) of the above distilledICH₂CH₂CF₂CF₂CF₂I was treated with 26 g Na₂S₂O₄ (MW=174, 91%, 0.136 mol)and 13 g NaHCO₃ (MW=84, 0.154 mol) in 50 g CH₃CN and 68 g H₂O at roomtemperature for 2 hrs. ¹⁹F NMR analysis of the reaction solution showedcomplete conversion of —CF₂I (−67 ppm) to form the corresponding—CF₂SO₂Na at ˜−130 ppm yielding the desired ICH₂CH₂(CF₂)₃SO₂Na. Themixture was filtered to remove solids. The filtered solution showed twophases, and only top phase showed fluorinated product based on ¹⁹F NMRanalysis. The top phase was separated, and the solvents were removed byrotary evaporation to give 48 g wet solid. The wet solid was dissolvedin water and the following chemical shifts were recorded and confirmedthe designed product. ¹⁹F NMR of ICH₂CH₂CF₂CF₂CF₂SO₂Na: −115 ppm (dxtxt,2F, —CF2CH2-), −124 (m, 2F), −130 (t, 2F, —CF2SO2M); 1H NMR ofICH₂CH₂CF₂CF₂CF₂SO₂Na: 3.2 ppm (txm, 2H, —CF2CH2-), 2.5-3.0 (m, 2H,—CH2I).

The above ICH₂CH₂(CF₂)₃SO₂Na wet solid was dissolved in ethanol andtreated with 8.7 g KOH (MW=56, 85%, 0.132 mol) at room temperature, thenthe mixture was reacted at 50° C. for 8 hrs to precipitate a solid (KI).The reaction mixture was cooled to 20° C. and filtered to remove solids.No significant change in ¹⁹F NMR was observed. The solvent was strippedand the resulting solid was acidified with 2NH₂SO₄ to a pH<2. Theacidified solution was extracted with t-butylmethyl ether (three times,100 mL each) and the combined ether solution was dried over MgSO₄.Finally, the solution was filtered and the solvent was stripped to yield21.5 g (MW=242, 88.8 mmol) desired semisolid product, CH₂═CH(CF₂)₃SO₂H,which is soluble in water. The structure of the product was confirmed byNMR analyses, ¹⁹F NMR, −115 (dxt, 2F, ═CHCF2-), −125 (txm, 2F), −127 (t,2F, —CF2SO2H). ¹H NMR, 4.4˜5.6 (m) ppm, indicating no more ICH₂CH₂—signal. The isolated yield is ˜88.8% from ICH₂CH₂CF₂CF₂CF₂I.

Synthesis of FKM6

The polymerization was carried out as with FKM4 with the followingchanges. 10 g of CH₂═CH(CF₂)₃SO₂H (in an 8% aqueous solution) was usedin place of MV4SO₂NH₄. The reactor was also heated to 80° C. The meanparticle size in the latex was 243 nm and the resulting fluoroelastomerraw gum had a Mooney viscosity of 50 at 121° C. The fluoroelastomer byFT-IR analysis contained 80.2 mol % copolymerized units of VDF and 19.8mol % HFP. The fluorine content was 65.4 wt %.

Synthesis of FKM7

A 4 liter reactor was charged with 2,250 g water, 1.7 g diethyl malonate(DEM), an aqueous solution containing 5.2 g ammonium persulfate (APS,(NH₄)₂S₂O₈), 5.0 g potassium phosphate dibasic (K₂HPO₄), and 17.6 g ofthe MV4SO₂NH₄ vinyl sulfinate monomer (ammonium salt). Containers fromwhich the solid reagents were added were rinsed, and the rinse water,totaling 425 g, was added to the reactor. The reactor was evacuated; thevacuum was broken and the vessel was pressurized with nitrogen to 25 psi(0.17 MPa). This evacuation and pressurization cycle was repeated threetimes. After removing oxygen, the reactor was heated to 73.9° C. andpressurized with 22 g hexafluoropropylene (HFP). The reactor was thencharged with 139 g vinylidene fluoride (VDF) and 109 grams ofhexafluoropropylene (HFP). The reactor was agitated at 650 rpm. Asreactor pressure dropped due to monomer consumption in thepolymerization reaction, HFP and VDF were continuously fed to thereactor to maintain the pressure at 160 psi (1.11 MPa). The ratio of HFPand VDF was 0.651 by weight. After 752.5 grams of VDF had beenintroduced, the monomer feeds were discontinued and the reactor wascooled. The resulting dispersion had a solid content of 33.9 wt % and apH of 3.4. The mean particle size in the latex was 141 nm and the totalamount of dispersion was about 4,027 grams.

The coagulation was done according to the method described under“Synthesis of FKM4”.

Materials

Material Name Description MV4S CF₂═CF—O—C₄F₈—SO₂F, made as described inthe Example (section A to C) of U.S. Pat. No. 6,624,328 (Guerra)MV4SO2H/ CF₂═CFOC₄F₈SO₂H synthesized as per “MV4SO2H/ MV4SO2NH4MV4SO2NH4 SYNTHESIS” I(CF₂)₃I May be obtained by distillationpurification from the reaction mixture of U.S. Pat. No. 6,002,055example 6. PPA3 A synergistic polyethylene glycol and branchedfluoroelastomer blend commercially available as “DYNAMAR FX-5930 from 3MCompany, St. Paul, MN. The branching is accomplished without sulfinates.FKM 4 Branched fluoroelastomer dipolymer prepared with MV4SO2NH4 as per“SYNTHESIS OF FKM4” FKM5 Linear fluoroelastomer prepared according tothe “SYNTHESIS OF FKM5” FKM6 Branched fluoroelastomer dipolymer preparedwith CH₂═CH(CF₂)₃SO₂H as per “SYNTHESIS OF FKM6” FKM7 Branchedfluoroelastomer made via batch addition of MV4SO2NH4 as per “SYNTHESISOF FKM7” PPA1 A 70 MV fluoroelastomer prepared as per “SYNTHESIS OFPPA1”. PPA2 A synergistic polyethylene glycol and fluoroelastomer blendcommercially available as “DYNAMAR FX 5920A” from 3M Company, Maplewood,MN) 2MI LLDPE A Linear Low Density Polyethylene commercially availableas “LL 1002.09” from ExxonMobil Chemical Company, Houston, TX 0.9MILLDPE A Linear Low Density Polyethylene commercially available as“MARFLEX 7109” from, Chevron Phillips Chemical Company, The Woodlands,TX Talc 60% talc in polyethylene (“ABT-2500”) concentrate, commerciallyavailable as “AMPACET # 101558” from Ampacet, Tarrytown, NY Erucamide 5%erucamide in polyethylene concentrate, commercially available as“AMPACET # 10090” from Ampacet, Tarrytown, NY Purge compoundCommercially available as “POLYBATCH KC-30” from A. Schulman, Akron, OHAntioxidant Commercially available as “IRGANOX B-900” from BASFCorporation, Florham Park, NJ Acid neutralizer Commercially available as“ZINC STEARATE # 33238” from Alfa Aesar, Ward Hill, MA

TABLE 1 log Eta Temp. Zero Mooney ° C. MV4S @265° C. Vis- IV η (° F.) gPa · s cosity dL/g mL/g LCBI FKM7 74 17.6 4.90 56 0.31 31  NM* (165)FKM4 73 15 6.39 55 0.87 89 2.2 (164) PPA1 71 — 5.81 70 NM NM 0.0 (160)FKM NM — 3.09 33 NM NM 0.0 from PPA2 FKM NM — NM 42 0.89 NM ~5   fromPPA3 FKM5 74 — NM 55 NM NM NM (165) FKM6 74 — 3.98 50 NM NM NM (165) NM= not measured *NM = not measured due to poor solubility of theelastomer

Example 1

A concentrate comprising 3% of a branched elastomer FKM4 with a Mooneyviscosity of 55 was prepared according to the method described above. Itwas tested on the Keifel film line as described, at a level of 350 ppm,in a 0.9 MI LLDPE formulation containing 6000 ppm of talc and 1000 ppmof erucamide. Melt fracture was eliminated in 50 min.

Comparative Example 1

A linear elastomer FKM5 with a Mooney viscosity of 55 was tested underthe conditions of Example 1. Melt fracture was eliminated in 80 min.

Comparative Example 2

A commercial linear elastomer PPA1 with a Mooney viscosity of 68 wastested under the conditions of Example 1. Melt fracture was eliminatedin 60 min.

Example 2

A branched elastomer FKM6 with a Mooney viscosity of 50 was prepared.

TABLE 2 % Melt Fracture Remaining vs. Time Time (min) EX1 CE1 CE2 0 100100 100 10 100 100 100 20 77 100 78 30 18 60 7 40 2 21 2 50 0 9 0.5 60 30 70 1 80 0 90 100 110 120

Example 3

A concentrate comprising 1.5% of a branched elastomer FKM4 and 1.5% ofpolyethylene glycol (3% PPA) was prepared according to the methoddescribed above. It was tested on the Keifel film line as described, ata level of 250 ppm, in a 0.9 MI LLDPE formulation containing 7500 ppm oftalc and 1500 ppm of erucamide. Melt fracture was eliminated in 80 min.

Example 4

A concentrate comprising 1.5% of a moderately branched elastomer FKM7and 1.5% of polyethylene glycol (3% PPA) was prepared according to themethod described above. FKM7 was made with sulfinate added batchwiseunlike the continuous addition with FKM4. The concentrate was tested onthe Keifel film line as described, in a 0.9 MI LLDPE formulationcontaining 7500 ppm of talc and 1500 ppm of erucamide. For thisevaluation, the PPA was added at a level of 250 ppm for the first hourand increased to 400 ppm afterward. 47% melt fracture remaining after 90min.

Comparative Example 3

A 3% concentrate of PPA2 was tested under the conditions of Example 3,with the exception that the PPA level was 1500 ppm. 100 min wererequired to eliminate melt fracture.

Comparative Example 4

A concentrate comprising 3% PPA3 was tested under the conditions ofExample 3. Melt fracture was eliminated in 60 min.

Comparative Example 5

A 3% concentrate of PPA1 was tested under the conditions of Example 4.There was 8% melt fracture remaining after 120 min.

TABLE 3 % Melt Fracture Remaining vs. Time Time (min) EX3 EX4 CE3 CE4CE5 0 100 100 100 100 100 10 100 100 100 100 100 20 87 100 100 80 100 3058 99 92 30 95 40 29 97 71 4 85 50 13 90 50 1 70 60 4 85 29 0 65 70 1 757 31 80 0 64 0.5 28 90 47 0.5 20 100 0 14 110 8 120 8

Foreseeable modifications and alterations of this invention will beapparent to those skilled in the art without departing from the scopeand spirit of this invention. This invention should not be restricted tothe embodiments that are set forth in this application for illustrativepurposes. To the extent that there is a conflict or discrepancy betweenthis specification and the disclosure in any document incorporated byreference herein, this specification will control.

What is claimed is:
 1. A melt-processible polymer compositioncomprising: a non-fluorinated melt-processible polymer; and afluorine-containing polymer derived from the polymerization of a monomerand a sulfinate-containing molecule, wherein the sulfinate-containingmolecule is selected from the group consisting of:

wherein X₁, X₂, and X₃ are each independently selected from H, F, Cl, aC₁ to C₄ alkyl group, and a C₁ to C₄ fluorinated alkyl group; R is alinking group; Z₁ and Z₂ are independently selected from F, CF₃, and aperfluoroalkyl group; R₁ and R₂ are end-groups; p is 0 or 1; m is atleast 2; and M is a cation.
 2. The melt-processible polymer compositionof claim 1, wherein the sulfinate-containing molecule of Formula (I) isselected from: CF₂═CF—O(CF₂)_(n)—SO₂M; CH₂═CH—(CF₂)_(n)—SO₂M; CF₂═CF—O[CF₂CF(CF₃)O]_(n)(CF₂)_(o)—SO₂M; and combinations thereof, where n is atleast 1, o is at least 1, and M is a cation.
 3. The melt-processiblepolymer composition of claim 1, wherein the sulfinate-containingmolecule of Formula (II) comprises a segment selected from the groupconsisting of:

and combinations thereof, where n is at least 1, o is at least 1, and mis at least
 1. 4. The melt-processible polymer composition of claim 1,wherein the fluorine-containing polymer has an LCBI of greater than 0.2.5. The melt-processible polymer composition of claim 1, furthercomprising a synergist.
 6. An article comprising the melt-processiblepolymer composition of claim
 1. 7. The melt-processible polymercomposition of claim 5, wherein the synergist is polyethylene glycol orpolycaprolactone.
 8. The melt-processible polymer composition of claim1, wherein the fluorine-containing polymer is further derived from asecond fluoroalkyl sulfinate initiator.
 9. The melt-processible polymercomposition of claim 8, wherein the second fluoroalkyl sulfinateinitiator is C₄F₉SO₂M, wherein M is a cation.
 10. The melt-processiblepolymer composition of claim 1, wherein the monomer is selected from:tetrafluoroethylene, hexafluoropropylene, trifluoroethylene vinylidenefluoride, vinyl fluoride, bromotrifluoroethylene,chlorotrifluoroethylene, CF₃CH═CF₂, C₄F₉CH═CH₂, CF₂═CHBr, CH₂═CHCH₂Br,CF₂═CFCF₂Br, CH₂═CHCF₂CF₂Br, and combinations thereof.
 11. Themelt-processible polymer composition of claim 1, wherein thefluorine-containing polymer is crystalline.
 12. The melt-processiblepolymer composition of claim 1, wherein the fluorine-containing polymeris semi-crystalline, or amorphous.
 13. The melt-processible polymercomposition of claim 1, wherein the fluorine-containing polymer ispartially fluorinated.
 14. The melt-processible polymer composition ofclaim 1, wherein the fluorine-containing polymer is fully fluorinated.